Pesticidal compositions and methods containing 2 - (o o-dialkyl-phosphoryl)-6 - carbalkoxy or carbalkenoxy-pyrazolo-pyrimidines

ABSTRACT

A COMPOSITION CONTAINING, AS THE ACTIVE INGREDIENT, A COMPOUND OF THE FORMULA   2-(R1-O-P(=X)(-O-R2)-O-),5-(CH3-),6-R3-PYRAZOLO(1,5-A)   PYRIMIDINE   IN WHICH R1 AND R2 ARE ALKYL OR 1 TO 4 CARBON ATOMS, R3 REPRESENTS A CARBALKOXY OF UP TO 13 CARBON ATOMS OR CARBALLYLOXY, AND X STANDS FOR OXYGEN RO SULFUR, IS EFFECTIVE AGAINST PLANT-SUCKING AND PLANT-EATING INSECTS, ACARIDA SUCH AS SPIDER MITES AND TICKS IN ALL STAGES OF DEVELOPMENT INCLUDING THEIR EGGS, AS WELL AS AGAINST NEMATODES AND PHYTOPATHOGENOUS FUNGI.

United States Patent Ofice 3,632,757 Patented Jan. 4, 1972 Int. Cl. A01n9/36; A611 13/00 US. Cl. 424-200 10 Claims ABSTRACT OF THE DISCLOSURE Acomposition containing, as the active ingredient, a compound of theformula in which R, and R are alkyl of 1 to 4 carbon atoms, R representsa carbalkoxy of up to 13 carbon atoms or carballyloxy, and X stands foroxygen or sulfur, is effective against plant-sucking and plant-eatinginsects, Acarida such as spider mites and ticks in all stages ofdevelopment including their eggs, as well as against nematodes andphytopathogenous fungi.

in which R and R each represent a low molecular weight alkyl radicalhaving 1 to 4 carbon atom, R stands for carbalkoxy of up to 13 carbonatoms or carballyloxy, and X stands for oxygen or sulfur. They can beprepared by reacting phosphoric acid halides of the following formula PHal in which X, R and R have the meanings given above and Hal stands fora halogen atom, with a corresponding 2-hydroxy-pyrazolo-pyrimidine inthe presence of an acidbinding substance, for example, an alkali metalcarbonate or a tertiary base such as triethylamine or pyridine, or witha Z-hydroxy-pyrazolo-pyrimidine salt, for example an alkali metal saltthereof.

Among the compounds of Formula I that have shown unexpectedly goodefficacy as pesticides, special mention should be made of those in whichR is a carbalkoxy or carbalkenoxy group. Compounds in which R iscarbomethoxy, carbethoxy, carbododecyloxy or carboallyloxy arepreferred.

The active ingredients can be prepared as indicated in the followingreaction equations x NN T/ J I Hal-P\ on. \N 0M6 3 z r oai CH3 N Thereaction may be carried out in the presence or absence of a solvent. Assolvents it is advantageous to use aliphatic ketones of low molecularweight, for example, acetone or methyl ethyl ketone, nitriles such asacetonitrile, esters such as acetic methyl ester, ethers such astetrahydrofurane or dioxane, chlorinated hydrocarbons such as CH Cl orcarbon tetrachloride, or aromatic substances such as benzene, xylene orsimple derivatives thereof such as chlorobenzene, dichlorobenzene ornitrobenzene.

The reaction generally proceeds with sufficient speed already at atemperature of about 15 to 25 C. It may be increased by raising thetemperature, for example, to 50 to 70 C. or to reflux temperature and/orby adding a small amount of copper powder.

The compounds obtained by the process of the invention are oils whichcannot be distilled without decomposition, or solid crystallineproducts.

The compounds of the invention are effective against plant-sucking andplant-eating insects, and Acarida, such as spider mites and ticks, inall stages of development, inclusively their eggs. They are alsoeffective against nematodes and phytopathogenous fungi.

The novel active substances are used in the usual mixtures with solid orliquid inert carrier materials, adhesives, wetting or dispersing agentsor grinding auxiliary agents as dusting or spraying preparations in theform of aqueous spraying liquids or emulsions, either alone or inadmixture with other active substances. They are effective as feedingand contact poison or in the form of vapor and have also a systemicaction.

It should be noted that the compounds of the invention have, in part, animproved action against pests and, in part, a lower toxicity towarm-blooded animals as compared with known commercial preparations, andthat they simultaneously have a fungicidal action.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto.

Analysis.-M (315). Calculated (percent): P, 9.8;N, 13.3. Found(percent): P, 9.7; N, 13.1.

48.9 g (0.3 mole) 2-hydroxy-5.7-dimothyl-pyrazolopyrimidine were addedto a solution of 0.3 mole sodium ethylate in 200 cc. ethanol. To theclear solution so obtained, 56.4 g. (0.3 mole)0,0-dicthyl-thiophosphoryl chloride were added dropwise. After stirringfor 2 hours at 50 to 50 C., the reaction mixture was separated from theprecipitated sodium chloride by suction filtration. After the ethanolhad been dis-tilled 011, the 2-(0,0- diethyl thiono phosphoryl) 5,7dimethyl pyrazolopyrimidine crystallized out from the filtrate.

After recrystallization from a mixture of benzene and petroleum ether,colorless scales melting at 45 C. were obtained. The yield amounted to75 g.

EXAMPLE 2 a Analysis-M (287). Calculated (percent): LP, 10.8; N, 14.6.Found (percent): P, 10.7; N, 14.6.

160.4 g. (1 mole) 0,0-dimethyl-thiophosphoryl-chloride were addeddropwise to a suspension of 185 g. (1 mole) of the sodium salt of2-hydr0xy-5.7-dimethylpyrazolo-pyrimidine in 800 cc. methyl ethylketone. The mixture so obtained was stirred for 1 hour at a roomtemperature of C. and then filtered. When the solvent was filtered 01f,2-(0,0-dimethyl-thiono-phosphoryl)-5.7- dimethyl-pyrazolo-pyrimidinecrystallized out from the filtrate.

A slightly yellow powder melting at 72 C. to 74 C. was obtained. Theyield amounted to 282 g.

EXAMPLE 3 48.9 g. (0.3 mole) 2-hydroxy-5.7-dimethyl-pyrazolopyrimidineand g. K CO were suspended in 100 cc. acetone. 48 g. (0.3 mole)0,0-dimethyl-thiophosphoryl chloride were added drop-wise while stirringand the reaction mixture washeated for 2 hours at 40 to 50 C. Afterfiltering 01f from the excess amount of K CO and KCl, 84 g.2-(0,0-dimethyl-thiene-phosphoryl)-5,7- dimethyl-pyrazolopyrimidinemelting at 72 to 74 C. were obtained from the acetonic solution.

EXAMPLE 4 A/mlysis.-M (365). Calculated (percent): P, 8.4; N, 11.5.Found (percent): P, 8.1; N, 11.1. t

g. (0.2 mole) 2-hydroxy-5-phenyl-7-methylpyrazolo-pyrimidine weresuspended in 200 cc. xylene. After the addition of 0.2 moletriethyiamine, 38 g. (0.2 mole) 0,0-diethyl-thiophospheryl-chloride wereadded dropwise. The mixture so obtained was heated for 3 hours at 80 C.and filtered off with suction from the triethylamino hydrochlorideformed.

From the filtrate, the 2-0,0-diethyl-thionophosphoryl)-5-phenyl-7-methyl-pyrazolo-pyrimidine was isolated.

68 g. of a viscous oil were obtained.

EXAMPLE 5 E N N AnaIysis.M (394). Calculated (percent): P, 7.8; N, 10.7.Found (percent): P, 7.4; N, 11.0.

26 g. (0.93 mole) of the potassium salt of 2-hydroxy- 3 bromo 5.7dimethyl pyrazolo pyrimidine were suspended in 250 cc. tetrahydrofurane.17.7 g. (0.93 mole) 0,0-diethyl-thiophosphoryl chloride were then addeddropwise. The reaction mixture was heated for 4 hours under reflux, andfiltered off with suction from the KCl which had separated. Thetetrahydrofiurane was then distilled off from the filtrate.

As residue 2 (0,0 diethy lthiono phosphoryl) 3-bromo-S.7-dimethyl-pyrazolo-pyriniidine was obtained. The yield amountedto 36.5 g. The product constituted a viscous yellow oil which solidifiedafter some time.

EXAMPLE 6 Analysis.M (317). Calculated (percent): P, 9.7; S, 10.1. Found(percent): P, 10.1; S, 10.3.

22 g. (0.12 mole) of the sodium salt of 2.7-dihydroxy-5-methyl-pyrazolo-pyrimidine were suspended in 200 cc. acetic acidmethyl ester. About 0.5 g. copper power was added and 23 g. (0.12 mole)O,O-diethyl-thiophosphoryl chloride were dropped in. The mixture soobtained was heated for 4 hours under reflux and filtered, and thesolvent was then removed from the filtrate.

As residue, 28 g. 2-(O,O-diethyl-thiono-phosphoryl)-S-methyl-7-hydroxy-pyrazolo-pyrimidine were obtained in the form of aviscous red oil.

EXAMPLE 7 Analysis.M (343). Calculated (percent): P, 9.05; N, 12.2.Found (percent): P, 8.9; N, 12.2.

A mixture of 0.225 mole (48 g.) of the sodium salt of 2hydroxy-S-methyl-6-acetyl-pyrazolo-pyrimidine, about 0.5 g. copperpowder, 42.5 g. (0.225 mole) 0,0-diethylthiophosphoryl chloride and 200cc. acetone was stirred for 2 hours at 40 to 50 C. The filtrate wasfreed from the NaCl which had been formed, and concentrated, the residuewas dissolved in methylene chloride and washed with a 2 N-soda solutionand water.

After distilling off the methylene chloride, 68 g. 2-(0,0-diethyl-thiono-phosphoryl)-5-methyl 6 acetyl-pyrazolopyrimidine wereobtained from the organic phase in the form of a non-distillable oil.

EXAMPLE. 9 5

Analysis.M (271). Calculated (percent): P, 11.4; N, 15.5. Found(percent): P, 11.0; N, 15.5.

44 g. (0.3 mole) 0,0-dimethyl-phosphoryl chloride were added dropwise to56 g. (0.3 mole) of the sodium salt of2-hydroxy-5,7-dimethyl-pyrazolo-pyrimidine in 200 cc. methylenechloride. During this procedure the temperature rose from 20 C. to 38 C.The mixture was then stirred for 2 hours at a room temperature of 20 C.The filtrate was freed from NaCl and washed as described in Example 8.

By removing the solvent, 80 g.2-(0,0-dimethyl-phosphoryl)-5.7-dimethyl-pyrazolo-pyrimidine wereobtained in the form of a colorless powder melting at 79 C. to 81 C.

EXAMPLE 10 Analysis.M (343). Calculated (percent): P, 9.0; N, 12.2.Found (percent): P, 8.5; N, 11.8.

3.8 g. (0.094 mole) NaOH were dissolved in 200 cc. methanol. To thesolution so obtained, 18 g. (0.094 mole) 2 hydroxy S-isopropyl 7 methypyrazolo-pyrimidine were added. From the resulting clear solution themethanol was distilled off, the residue was taken up in acetone, and asmall amount of copper powder and 18 g. (0.095 mole)0,0-diethyl-thiophosphoryl chloride were added. The mixture so obtainedwas stirred at 50 C. for 2 hours and Worked up as described in Example8.

25 g. 2-(0,0-diethyl thiono-phosphorpyl)-5-isopropyl-7-methyl-pyrazolo-pyrimidine were obtained in the form of a yellow oilwhich soldified on cooling down to -20 C.

EXAMPLE 1 l Analysis.M (373). Calculated (percent): P, 8.3; S, 8.6.Found (percent): P, 8.0; S, 6.5.

A mixture of 24.3 g. (0.1 mole) of the sodium salt of 2-hydroxymethyl-7-carbethoxy-pyrazolopyrimidine, 18.9 g. (0.1 mole)0,0-diethyl-thiophosphoryl chloride and 200 cc. acetone was stirred atabout 50 C. for 8 to hours. From the filtrate which had been freed fromNaCl, 37 g. 2-(0,0-diethyl-thionophosphoryl) 5 methyl-6-carbethoxy-pyrazolo-pyrimidine were obtained in the form of a yellow oil(melting point 38 C. to 40 C.).

EXAMPLE 12 EXAMPLE 13 Analysis.-M (345). Calculated (percent): P, 9.0;S, 9.3. Found (percent): P, 8.6; S, 9.7.

The process was carried out in a manner analogous to that described inExample 11 (0.1 molar), but while using, instead ofdiethyl-thiophosphoryl chloride, 0,0-dimethyl-thiophosphoryl chloride(0.1 mole=16.1 g.). There were obtained2-(0,0-dimethyl-thiono-phosphoryl)-5-methyl 6carbethoxy-pyrazolo-pyrimidine in the form of a yellow wax-like compoundmelting at about 25 C. The yield was quantitative.

EXAMPLE 14 I T on, J\)-0P(OCH3),

Analysis.--M (329). Calculated (percent): P, 9.4; N, 12.8. Found(percent): P, 9.9; N, 12.4.

By proceeding in a manner analogous to that described in Example 11, butusing, instead of diethyl-thiophosphoryl chloride, 0.1 mole=14.7 g.dimethyl-phosphoryl chloride, there were obtained 32 g.2-(0,0-dimethylphosphoryD-S-methyl 6 carbethoxy-pyrazolo-pyrimidine inthe form of a red-brown oil.

EXAMPLE 15 omo-oc Analysis.-M (359). Calculated (percent): P, 8.6; N,11.7. Found (percent): P, 8.3; N, 11.0.

A mixture of 41.4 g. (0.2 mole) 2-hydroxy-5-rnethyl-6carbomethoxy-pyrazolo-pyrimidine, 37.8 g. (0.2 mole)diethyI-thiophosphoryl chloride, 22 g. (0.22 mole) triethylamine and 300cc. acetone was heated for 5 hours at 60 C. The triethylaminohydrochloride was then suction-filtered and the solvent was distilled01f.

67 g. 2-(0,0-diethyl-thionoph0sphoryl) 5 methyl-6-carbomethoxy-pyrazolo-pyrimidine were obtained in the form of a brownoil which solidified slowly.

EXAMPLE 16 Analysis.M (513). Calculated (percent): P, 6.1. Found(percent): P, 6.4.

23 g. (0.064 mole) 2-hydroxy 5methyl-6-carbododecyloxy-pyrazolo-pyrimidine were dissolved in 200cc.'acetone 12.5 g. (0.006 mole) diethyl-thiophosphoryl chloride and 8g. (0.08 mole) triethylamine were then EXAMPLE 17 cn -on-orno-oo sAnalysis.M (361). Calculated (percent): P, 8.6; N, 11.6. Found(percent): P, 8.3; N, 11.1.

A mixture of 23.3 g. (0.1 mole )Z-hydroxy-S-methyl--6-carballyloxy-pyrazolo-pyrimidine, 18.9 g. (0.1 mole)diethyl-thiophosphoryl chloride and 12 g. (0.12 mole) triethylamine in200 cc. methyl ethyl ketone was heated for 8 hours at 5 C. The filtratewas freed from triethylamino hydrochloride and evaporated. 35 g. 2 (0,0-diethyl thiono phosphoryl) 5 methyl 6 car boallyloxy-pyrazolo-pyrimidinewere obtained in the form of an oil which solidified slowly to yield awax.

EXAMPLE 18 A wettable powder was obtained by mixing the followingcomponents:

10% of 0,0-dimethyl-O-(5.7-dimethyl-pyrazolopyrimidyl-(2))-thiophosphoric acid ester 10% of active silicic acid 10% of aluminumsilicate 3.5% of alkyl-arylsulfonate as wetting agent 56.5% of sodiumsulfate 10% of cellulose pitch.

By suspending in water, a spraying liquid was obtained, which wasapplied in a concentration of 0.05%, i.e. with an active substanceconcentration of 0.005%.

In laboratory tests, small unripe apples were sprayed and eggs ofcodling moths (Carpocapsa pomonella) were placed near the apples so thatthe caterpillars could reach the apples of their own strength and seek aplace for boring into the apples as is the case in nature. The treatedapples were not infested and 100% of the caterpillars died, at thelatest on boring, even when up to eggs had been laid per apple and allthe caterpillars had hatched.

For a comparison, 0,0-diethyl-O-(2 isopropyl 4- methyl-pyrimidyl 6)thionophosphate (cf. Schrader Die Entwicklung neuer insektiziderPhosphorsaureester. 1963, Verlag Chemie, page 149) was used. With thesame active substance concentration of 0.005%, only 68% of thecaterpillars was destroyed and with twice the concentration (0.01%) only83%.

EXAMPLE 19 An aqueous spraying liquid obtained from a wettable powdercontaining 10% of 0,0-diethyl-O-(5 phenyl-7- methyl-pyrazolo-pyrimidyl(2)) thiophosphoric acid ester in a formulation analogous to that ofExample 18, was sprayed on cotton and lucerne infested with Prodenialitura. By applying the wettable powder in a concentration of 0.25%,i.e. by using 0.025% of active substance, further damage by thecaterpillars was prevented and the latter were destroyed the same day.Even in the case of large caterpillars of the fifth stage, destructionamounted to 100%.

EXAMPLE 20 A wettable powder containing 10% of 0,0-dimethyl- 0-(5.7dimethyl pyrazolo pyrimidyl (2)) thiophosphoric acid ester in aformulation analogous to that of Example 18 was used in aqueoussuspension against wheat mildew. With a concentration of 0.06% of activesubstance a destruction of 96% was obtained, and with a concentration of0.03% of active substance a destruction of In the case of bean mildew, adestruction of 97% was obtained with an active substance concentrationof 0.025% and a destruction of 92% with an active substanceconcentration of 0.012%.

EXAMPLE 21 Larvae of the fourth stage of African migratory locust(Pachytz'lus migratorius migratoriodies) were destroyed within a fewhours by spraying them directly with a 0.1% aqueous emulsion of anemulsifiable spraying preparation of the following composition:

10% of 0,0-diethyl-O-(5.7-dimethylpyrazolopyrimidyl-(Z) )-thiophosphoricacid ester 78% of ethanol 10% of an oxethylated alkylphenol 2% ofepichlorhydrine.

The corresponding dimethyl compound was completely effective againstthese larvae with an active substance concentration of 0.02%.

With the comparison substance 0,0-dimethyl 5 [4- 0x0 1,2,3 benzotriazine3(4H)-yl-methyl]-phosphorus dithioate (Schrader, l.c., page 176) adestruction of only 80% was obtained with 0.02% of active substance.This difference which may perhaps seem only insignificant is, however,important when regarding the difference in toxicity to warm-bloodedanimals. The acute oral LD 50 (lethal dose to 50%) for female albinorats was 62 mg./ kg. of the compound of the invention, while it was 10to 18 mg./kg. for Azinphos.

EXAMPLE 22 Plant-sucking pests, i.e. plant-lice, shield-lice and bugs,were destroyed with preparations of 0,0-dimethyl-O- (5.7dimethyl-pyrazolo-pyrimidyl (2) )-thioph0sphoric acid ester formulatedas described in Examples 18 and 21.

Dorlis fabae and Pyrethromyzus sanborni on Vicia faba and Chrysanthemumspecies were all dead a few hours after a single spraying with only0.00075% of active substance.

EXAMPLE 23 The systemic action of0,0-dimethyl-O-(5.7-dimethylpyrazolo-pyrimidyl-(Z))-thiophosphoric acidester could be seen when the substance, in a cotton bandage covered witha plastic sheet, was applied to the stalk of Vicia faba in theformulation of Example 21.

All the plant-lice (Doralis fabae) at the upper parts of the plant weredestroyed within a short time by an amount of active substance of only 1to 2 mg. in the bandage.

EXAMPLE 24 0,0 dimethyl O (5 .7-dimethyl-pyrazolo-pyrimidyl-(2))-thiophosphoric acid ester had a strong action on insects of theorder of Diptera. The action on Musca domestica having a polyvalentresistance was similar to that on normally sensitive Musca domestica. Ina Petri dish test in which each dish contained 1 cc. of a 0.01% solutionof 0,0-dimethyl-O (5.7 dimethyl-pyrazolopyrimidyl-(Z))-thiophosphoricacid ester in acetone and was swung until the solution had dried inorder to obtain a uniform distribution, flies placed in the dishes wereall in an irreversible dorsal position after 45 to 60 minutes. There wasonly little difference in promptness of action on normal and resistantflies of both sexes. Even after the open dishes had been aired for 4weeks, a 100% lethal action on both varieties of flies was observedafter a time of action of 3 hours.

EXAMPLE 25 0,0-diethyl O 5.7 dimethyl-pyrazolo-pyrimidyl- (2))-thiophosphoric acid ester admixed with whey cheese as a nutrientmedium for larvae of M usca domestica was lethal to the said pests in aconcentration of only 0.0001%. Even still lower concentrations used inan appropriate manner yielded high quotas of kill.

EXAMPLE 26 A powder preparation for stored grain consisting of 2% of 5methyl 2.7 bis (0,0-diethyl-thiono-phosphoryl) -pyrazolo-pyrimidine 6%of aluminum hydrosilicate and 92% of talcum was uniformly admixed inknown manner in a ratio of 1:1000 with wheat. It destroyed grain weevils(Calandra granaria), rice weevils (Calandra oryzae) and other storagepests.

EXAMPLE 27 Cockroaches (Phyllodromia germanica and Periplanetaamericana) died when they were placed on a floor which had been dustedwith a preparation consisting of 2% of 2 (0,0-diethylthiono-phosphoryl)5 methyl 7- hydroxy-pyrazolo-pyrimidine, 6% of aluminum hydrosilicateand 92% of talcum in an amount of 1 to 2 g./m.

EXAMPLE 2-8 Blood-sucking Ornithodorus moubata was destroyed with0,0-diethyl-O-(3 bromo 5.7 dimethyl pyrazolopyrimidyl (2))thiophosphoric acid ester in the form of an emulsion (2% of aformulation with 10% of active substance, 78% of ethanol, 10% of ahighly concentrated oxethylated alkyl phenol and 2% ofepichlorohydrine).

EXAMPLE 29 Eggs of flour moths (Anagasta kuehniella) died when they camein contact with a 1% emulsion in water of a formulation containing 10%of 0,0-diethyl O (5.7-dimethyl-pyrazolo-pyrimidyl (2)) thiophosphoricacid ester, 78% of ethanol, 10% of a highly concentrated oxethylatedalkyl phenol and 2% of epichlorhydrine.

EXAMPLE 30 Soil strongly infested with nematodes of the generaPratylenchus, Paratylenchus and Rotylenchus, was freed therefrom byapplying the following formulation:

10% of 0,0-dimethyl O(5.7-dimethyl-pyrazolo-pyrimidyl-(2))-thiophosphoric acid ester 10% ofactive silicic acid 10% of aluminum silicate 10% of cellulose pitch56.5% of sodium sulfate 3.5% of alkyl-aryl sulfonate as wetting agent.

50 cc. water containing 1 g. of the above formulation were poured on 200cc. of the soil in an open container; 0.1 g. of active substance wassufficient for destroying the nematodes.

EXAMPLE 31 Cucumbers of a variety which was susceptible to mildew werestrongly infested artifically with a conidium suspension of cucumbermildew (Erysiphe cichoracearum). Five days after infestation, thecucumbers were treated with an aqueous emulsion of a preparation of thefollowing composition:

centrations of active substance under the same conditions ofapplication. Furthermore, untreated cucumbers were used for a control.

The test result obtained 3 Weeks after the treatment is indicated in thefollowing table. It clearly shows the excellent effect of the activesubstance of the invention against mildew. While the phophoric acidester in accordance with the invention, in concentrations down to 30 mg.of active substance per liter of spray liquor, completely preventedinfestation with mildew, the comparison substance used in the sameconcentrations could not prevent total infestation. Even when thecomparison substance was used in the highest concentration of 500 mg.per liter of spray liquor, infestation with mildew was 20%.

TABLE Percent of infestation with mildew with mg. of active substanceper liter of spray liquor Preparation 500 250 120 60 30 15 7. 5

A 0 0 0 0 3. 1 5. 0 16. 0 Commercial preparation used for a comparison1O 20 38 60 70 100 100 Untreated 100 100 100 100 100 100 100 A =2-[OO-diethyl-thiondphosphoryl1-5-methyl-fi-carbethoxypyrazo lo-pyrimidine.

EXAMPLE 32 In a cubic box of a volume of l m. in which common flies(Musca domestica) had been placed, 2 cc. of a 0.05% solution of2-(0,0-diethyl-thiono-phosphonyl)-5-methyl-7- hydroxy-pyr azolo-(l.5a)-pyramidine in petroleum were sprayed at room temperature. All theflies turned irreversibly over on their backs and soon died.

For a comparison, the commercial preparation Trichlorphon was used. Ithad only an insignificant effect even when sprayed in the form of a 0.1%solution.

EXAMPLE 33 (Comparison test) (b) In an analogous manner a test wasperformed using a preparation of the following composition:

10% of 2-(0,0-diethyl thiono phosphoryl)-5-methyl-6- carballyloxypyrazolo (1.5a) pyrimidine (referred to as B in the following table) ofethyl alcohol 10% of emulsifier.

(c) In an analogous manner a test was performed using a preparation ofthe following composition:

10% of 2 (0,0-diethyl thiono phosphoryl)-5-methyl- 6-carbododecyloxypyrazolo (1.5a) pyrimidine (referred to as C in the following table) 80%of ethyl alcohol 10% of emulsifier.

TEST RESULTS ASCERTAI IIECI3I 14 DAYS AFTER INFESTA- Percent of kill ofmildew with concentrations of percent of active substance 1 l The abovetable shown that preparations A, B and C in accordance with theinvention were superior to comparison products I, II, III and IV in thecontrol of wheat mildew, i.e. an infestation with phytopathogenousfungi.

What is claimed is:

1. A pesticidal composition effective against insects, Acarida,phytophathogenic fungi and nematodes containing, as the activeingredient, a compound of the formula in which R and R are alkyl of l to4 carbon atoms, R represents a carbalkoxy of up to 13 carbon atoms orcarballyloxy, and X stands for oxygen or sulfur, in admixture with acarrier selected from the group consisting of an inert solid carrier andan inert liquid carrier.

2. A pesticidal composition effective against insects, Acarida,phytopathogenic fungi and nematodes containing as the active ingredient,a compound of the formula N \OR2 in which R and R are methyl or ethyland R is a carbalkoxy of up to 13 carbon atoms or carballyloxy, in ad-12' mixture with a carrier selected from the group consisting of aninert solid carrier and an inert liquid carrier.

3. A composition as defined in claim 2 containing, as the activeingredient, 2-(0,0-diethyl-thiono-phosphoryl)-S-methyl-6-carbethoxy-pyrazolo-pyrimidine.

4. A composition as defined in claim 2 containing, as the activeingredient, 2-(0,0-dimethyl-thiono-phosphoryl-S-methyl-6-carbethoxy-pyrazolo-pyrimidine.

5. A composition as defined in claim 2 containing, as the activeingredient, 2-(0,0-diethylthiono-phosphoryl)-5-methyl-6-carbomethoxy-pyrazolo-pyrimidine.

6. A composition as defined in claim 2 containing, as the activeingredient, 2-(0,0-diethylthiono-phosphoryl)-S-methyl-6-carbododecyloxy-pyrazolo-pyrirnidine.

7. A composition as defined in claim 2 containing, as the activeingredient, 2-(0,0-diethyl-thiono-phosphoryl)-S-methyl-6-carboallyloxy-pyrazolo-pyrimidine.

8. A method of combatting pests selected from the group consisting ofplant sucking insects, plant eating insects and Acarida which consistsof applying to the locus infested by said pests a pesticidally effectiveamount of the composition of claim 1.

9. A method of combatting phytopathogenic fungi by applying to the locusinfested by said fungi a fungicidally effective amount of thecomposition of claim 1.

10. A method of combatting nematodes which consists of applying to thelocus of said nematodes a nematocidally elfective amount of thecomposition of claim 1.

References Cited UNITED STATES PATENTS 8/1968 Schicke 260-2654 E 4/ 1970Miller et a1. 42420() X US. Cl. X.R. 42428, 357

